Mono-and tris(amino-loweralkoxy)-(alkyl)-polyoxyalkylene compounds and method of preparation

ABSTRACT

A PROCESS IS DISCLOSED FOR MANUFACTURING NOVEL AMINES COMPRISING REACTING AN OLEFIN NITRILE SUCH AS ACRYLONITRILE WITH VARIOUS POLYHYDROXY COMPOUNDS FOLLOWED BY HYDROGENATION OF THE NITRILE GROUP TO OBTAIN THE AMINES. SOME EXAMPLES OF THE AMINES PREPARED COMPRISE: (1) A-(3-AMINOPROPOXY-W-(N-BUTYL)-POLY-1,2-OXYPROPYLENE (2) A-W-BIS-(3-AMINOPROPOXY)-POLY-1,2-OXYPROPYLENE1,4-OXYBUTYLENE (3) A-W-BIS-(3-AMINOPROPOXY)-POLY-1,2-OXYPROPYLENE (4) A-W-BIS-(3-AMINOPROPOXY)-POLY-1,2-OXYBUTYLENE (5) 1,2,6-TRIS(A-(3-AMINOPROPOXY)-POLY-1,2-OXYPROPYL)HEXANE (6) 1,2,3-TRIS(A-(3-AMINOPROPOXY)-POLY-1,2-OXYPROPYL) PROPANE (7) THE TRIS (3-AMINOPROPOXY)-ETHER OF OXYPROPYLATED TRIS-(4-HYDROXYPEHNYL)PROPANE THE HYDROGENATION IS ADVANTAGEOUSLY CONDUCTED IN THE PRESENCE OF A TERTIARY AMINE SUCH AS TRIMETHYLAMINE, MIXTURES OF A TERTIARY AMINE AND AMMONIA OR AMMONIA WHEN THE NITRILE IS FREE FROM POLYMERIC NITRILES. THE AMINES ARE USEFUL AS COMPONENTS OF POLYURETHANE ELASTOMERS, POLYURETHANE FOAMS, FLEXIBLE AND RIGID POLYAMIDE RESINS AND EPOXY RESIN HARDENERS.

United States Patent 3,799,986 MONO- AND TRIS (AMINO-LOWERALKOXY)- (ALKYL)-POLYOXYALKYLENE COMPOUNDS AND METHOD OF PREPARATION Fedor Poppelsdorf, Charleston, W. Va., assignor to Union Carbide Corporation No Drawing. Application June 26, 1963, Ser. No. 290,578, which is a continuation-in-part of applications Ser. No. 107,060, May 2, 1961, and Ser. No. 230,253, Oct. 12, 1962, all now abandoned. Divided and this application Dec. 8, 1967, Ser. No. 689,004

Int. Cl. C07c 93/02, 95/02, 121/38 US. Cl. 260-584 B 17 Claims ABSTRACT OF THE DISCLOSURE A process is disclosed for manufacturing novel amines comprising reacting an olefin nitrile such as acrylonitrile with various polyhydroxy compounds followed by hydrogenation of the nitrile group to obtain the amines. Some examples of the amines prepared comprise:

The hydrogenation is advantageously conducted in the presence of a tertiary amine such as trimethylamine, mixtures of a tertiary amine and ammonia or ammonia when the nitrile is free from polymeric nitriles.

The amines are useful as components of polyurethane elastomers, polyurethane foams, flexible and rigid polyamide resins and epoxy resin hardners.

This application is a divisional application of Ser. No. 290,578, entitled Nitrile Compositions by Fedor Poppelsdorf, filed June 26, 1963, now abandoned which is a continuation-in-part of Ser. No. 107,060 filedMay 2, 1961 and now abandoned and Ser. No. 230,253 filed Oct. 12, 1962, and now abandoned. I

This invention relates to novel beta-cyanoalkyl ethers of polyoxyalkylene adducts of moderately high molecular weight, derivatives thereof, and to compositions con.- taining the same. Y i

The cyano products of this invention are characterizable as a recurrent branched-chain oxyalkylene structure extending from an organo radical. These products desirably comprise recurring polyoxy-1,2-alkylene units, e.g., at leat two units, in a molecular chain terminated at least one end thereof by a beta-cyanoalkyl moiety. A significant aspect of this invention is that at least 50 percent of the oxyalkylene units are 1,2-oxyalkylene where the alkylene moiety has a pendant monovalent organic group positioned beta to an oxy moiety.

The products of this invention are more specifically characterized as a mixture of molecules containing betacyanoalkyl moieties and divalent dioxy-terminated polyoxyalkylene moieties. It is particularly desirable that the mixture have an average molecular weight of at least about 450. The divalent dioxy-terminated polyoxyalkylene moiety should be sufficiently present to comprise at least about 10 percent by weight of the mixture. More" over, the beta-cyanoalkyl moieties should be at least80 percent, up to 100 percent, of the molar quantity of the divalent polyoxyalkylene moieties.

In terms of more specific structural association of the components of the mixture, the divalent dioxy-terminated polyoxyalkylene moiety consists of recurring units of alkylenev oxide. At least 50 percent of these units are 1,2- oxyalkylene where the alkylene moiety thereof has a pendant monovalent hydrocarbon group positioned beta to an oxy moiety. Substantially, each of the divalent polyoxyalkylene moieties (at least 80 percent of the moieties) are joined at one free valence of the terminal oxy portion with one of the beta-cyanoalkyl moieties by a noncarbonyl (ether) linkage and at the free valence of the other terminal oxy portion with an organic chain-extending radical or an organic chain-blocking radical by a similar ether linkage. These radicals may comprise up to about 80 percent by weight of the mixture. The organic chain-extending radical is a poly-free valence bearing organic radical where each of the free valences is that of a different carbon atom of the radical and at least two of the free valence carbon atoms are joined to polyoxyalkylene moiety with any remaining free valences of the radical bonded directly to hydroxyl groups. On the other hand, the organic chain-blocking radical is a monovalent organic radical where the free valence is that of a carbon atom of the radical.

' The organic chain-extending radical serves the function of interlinking at least two polyoxyalkylene moieties through the radical. The radical is the residue of a polyhydroxy organic compound where at least two of the hydroxyl groups thereof are removed forming the free valences for chain extension. However, this definition is not intended to imply that chain extension is achieved by actual removal of the hydroxyl groups of the compound, but rather that the radical is definable as the residue of the compound by deleting the hydroxyl groups.

The radical may be obtained from a wide variety of polyhydroxy organic compounds, desirably one having armolecul'ar weight of at least about 62, typically not in excess of about 425. The compound may contain atoms other than carbon, oxygen and hydrogen, so long as these atoms are part of the eventual radical and are devoid of substituent groups or atoms capable of cleavage from the radical'in the. presenceof an alcohol lllustrative of the variety of the compounds are, e.g., bis(gamma-hydroxypropyl) dimethyl silane, bis(4-hydroxyphenyl)diethyl silane, pyrogallol, cyanuric acid, tris(2-hydroxyethyl) phosphine oxide, triethanolamine, and the like. However, the most preferred compounds are those which solely contain carbon, hydrogen and oxygen where oxygen is in the residue or is solely part of the hydroxyl groups. Further illustration of these preferred compounds is made below.

The organic chain-blocking radical, as pointed out previously, is monovalent where the free valence is that of a carbon atom of the radical. This radical, as is the similar case with the chain-extending radical, is definable as the residue of a monohydroxylated compound, i.e., the hydroxyl group is deleted from the compound to form the radical. This radical may be obtained from a wide variety of monohydroxy organic compounds and desirably is from one having a molecular weight of at least about 32, though typically not in excess of about 400. The monohydroxy compound may contain atoms other than carbon, hydrogen and oxygen, so long as these atoms are part of the eventual radical and are devoid of substituent groups or atoms capable of cleavage in the presence of an alcohol. Illustrative of the compounds are, e.g., gamma- 3 hydroxypropyl trimethyl silane; 4-hydroxyphenyl triphenyl silane; the mono alkyl ethers of ethylene glycol, dipropylene glycol, tetraethylene glycol; dimethyl cyanurate; 2-hydroxyethyl dimethyl phosphine or phosphine oxide; N,N diethyl N-(2-hydroxyethyl)amine; and the like. However, the most preferred compounds are those which solely contain carbon, hydrogen and oxygen where oxygen is in the residue or is solely part of the hydroxyl group.

The particularly preferred cyano substituted ethers of this invention are characterized by the formula:

Q is a dioxy (-O') terminated polyoxyalkylene radical having recurring units of the structure -dH-CH0, alone, or combined with units of the structure I CH(CH O, so long as at least fifty percent of the units of said polyoxyalkylene radical are R! -(JHOHzO-,

said polyoxyalkylene radical having an average of from about 6 to 250 of said recurring units, preferably an average of from about 10 to 150 of said recurring units; p is an integer of at least 1 and which preferably is equal to the free valence of the radical A and typically is an integer of from 1 to 10, v is an integer equal to the free valence of the radical A minus the value of p and typically is a value of from to 4; r is an integer of at least 1 and not greater than the value of p and r typically has an average value of at least 80 percent of that of p, preferably at least 90 percent of that of p; each R and R may be one of hydrogen, an alkyl group of from 1 to 18 carbon atoms, preferably from 1 to 4 carbon atoms, cycloalkyl of from 5 to 7 carbon atoms, or an aryl group; R may be an alkyl group of from 1 to 18 carbon atoms, preferably from about 1 to 4 carbon atoms, cycloalkyl of from 5 to 7 carbon atoms, or an aryl group; X and X may be hydrogen or an alkyl group, particularly of from 1 to 8 carbon atoms and preferably of from 1 to 4 carbon 4 atoms; y is an integer of from 0 to 10; m is an integer of from 0 to 8; b is an integer of from 1 to 3; g can be an integer of from 1 to 10; k is one of the integers 0 and 1, and preferably is the integer 1 when R is alkyl, as defined above; h can be an integer of from 1 to 8; t is an integer of from 2 to 4; c is a number having an average value of at least 2; M is a radical which can be alkyl, aralkyl,

O is the integer 0 or 1; R is a monovalent organic radical wherein the free valence is supplied by a carbon atom of said radical, for example, R may be alkyl (1 to 18 carbon atoms), monoether of a glycol residue, cycloalkyl (4 to 12 carbon atoms), aryl, alkaryl, and aralkyl; B is hydrogen or an alkyl group of from 1 to 4 carbon atoms; L is B or wherein the free valence of the R4 JH(CHz)rgroup is the valence bond of L; d, d and d" are each equal to 4 or 10; f is either a value of 0 or 1; and R is methyl when 1 is 0 and hydrogen whenf is 1. It is to be noted that A in the above formula encompasses the chainextending or chain-blocking radicals discussed previously.

The above compositions possessing molecular weights of at least about 450 and up to 20,000 and more, are typically found to have desirable biological activity suitable for agricultural use.

Moreover, these unique polymeric cyano-ether compounds are significantly desirable intermediates for producing corresponding amines, carboxylic acids, and carboxylic acid esters. The amine is readily produced by bydrogenation of the aforementioned beta-cyano ethers, particularly in accordance with the techniques described herein, resulting in the production of the corresponding gamma-amino ethers. On the other hand, the beta-cyano ethers may be hydrolyzed in accordance with well-known techniques to convert the cyano group to carboxylic whereby to produce a beta-carboxy ether corresponding to the above formula except that the cyano group is carboxy.

The ester may be formed by conventional direct esterification from the reaction of the nitrile group with a hydroxylated organic compound in the presence of an anhydrous mineral acid (such as HCl) followed by water addition. 1

The amino, carboxylic acid and ester products, particularly those having molecular weights of at least 450, may be used as lubricating oils for the purpose of lubricating moving frictional surfaces, as components in the manufacture of resinous products through reaction of the amino or carbonyloxy groups with other complimentary polyfunctional compounds such as polyisocyanates, polyols, polycarboxylic acid, their anhydrides and acid halides, polyepoxides, and the like. The aminoether derivatives have been found significantly desirable in the manufacture of foams when reacted with polyisocyanates.

As mentioned above, the cyano ethers of this invention have useful properties of biological purposes, especially in the field of fungicides. These compounds possess a wide range of fungicidal activity with a high level of performance. The novel beta-cyanoethyl ethersmay be used alone or in conjunction with other fungicidal and insecticidal agents, and can be formulated with inert diluents or carriers and applied as granules, powders, dusts, solutions or suspensions therein, for effective use on desirable plant life to eradicate or prevent the growth of a broad spectrum of parasitic fungi without deleterious effects upon the hosts, particularly as host in foliage.

"These beta-cyanoalkyl ethers may be prepared by contacting, in the presence of a basic condensing agent, a hydroxylated adduct of an alkylene oxide with hydroxy coinpounds, such as R-CH-OH pentaerythritol and/or others described herein (R, R, m, B, L and y are defined above), with an olefinically unsaturated hydrocarbon nitrile wherein the ethylenic group is conjugated with the nitrile group, such as an ethylenically unsaturated aliphatic hydrocarbon nitrile, e.g., acrylonitrile and/or its substituted derivatives, such as u-alkyl substituted acrylonitrile (e.g., methacrylonitrile, a-ethyl acrylonitrile, a-propylacrylonitrile, u-octyl acrylonitrile) and fl-alkyl acrylonitrile (e.g., crotononitrile, and the like) for a period of time sufficient to form the corresponding beta-cyanoalkyl ether addition products. The residues of these hydroxy compounds form the chainextending or chain-blocking radicals discussed previously. The cyanoalkylation of the hydroxylated adducts generally proceeds smoothly at around room temperature. However, reaction temperatures within the range. of from about 0 C. or lower, to 100 C. or higher, are within the broad purview of this invention. The reaction is typically exothermal and the reaction mixture is advantageously intermittently cooled to minimize possibilities of undesirable side reactions.

While stoichiometric proportions of the polyols and nitrile reactants are desirable, as illustrated by the following representative equations relating to the use of poly- 1,2-oxypropylene:

(CH: CH CH NCCHzOHzO HCHzO qHCHZO (BHCHzO iCH CHQCN H2O (CHCHzOhCHzCHzCN an excess of either reactant can be employed. In the above formulae, n, z and w are positive integers, the sum of which is from about '8 to 250 preferably from about to 150; i is an integer of at least 2 and q is an integer of at least 6, the sum of i and q being from 8 to 250.

In preferred operation, the nitrile is added in small successive amounts to an agitated mixture of the hydroxylated component and a basic (alkaline) condensing agent. Although it is not necessary, the reaction can be conducted in an inert solvent or suspending medium. Dioxane, hexane, pentane, heptane, octane, benzene, tolu- 6 ene, tetrahydrofuran, triethylamine, pyridine, cyclohex: an, and the likesolvents can be employed for this purpose. 5

The basic agent may be employed in small'catalytic quantities so as to effect the reaction between the nitrile and the hydroxylated compound. Typically, the amount of basic ragent is from about'0.01 to about 5 weight percent, preferably from 0.05 to 2 weightpercent, of-the hydroxylated adduct component of the reaction-Examples of basic condensing agents include the alkali metal and droxides in aqueous solutions such as e.g., the alcoholates, oxides and the like of the aforementionedxmetals. Other condensing agents include the alkali metal amides such as sodamide and the product of the reaction of sodium and pyridine to form the corresponding amide structure; quaternar ammonium compounds such as benzyltrimethylammonium hydroxide, tetrakis(2-hydroxyethyl) ammonium hydroxide and the like; and anhydrous hydrides of the alkali metals and alkaline earth metals. In those cases where the hydroxyl grou'psof the hydroxylated adduct are predominantly secondary," the preferred basicagents "are the alkali metal hydroxides," alcoholates, oxides and the like When the reaction is conducted at about room temperature, the condensation is typically completed in less than 8 hours after terminating addition of acrylonitrile or any of the other nitrile components. The course of reaction may be followed by infrared analysis, the end point being indicated when'there is no further reduction in the absorption'band due to hydroxyl moiety. The basic condensing agent is advantageously neutralized by the addition to the reaction mixture of an acid, preferably phosphoric acid. Any unreacted acrylonitrile or other nitrile and water may be removed from the reaction mixture under reduced pressure at temperatures typically not exceeding about C. thereby leaving a still residue of desired betacyanoalkyl ether. The vacuum-stripping operation is advantageously continued until the weight of the residue remains constant. In most cases, when prepared by the aforedescribed method, special purification steps other than those described herein may be avoided. Usually, the product is a clear and almost colorless oil.

The hydroxylated adduct starting materials which are reactable with the aforementioned ethylenically unsaturated nitriles are obtainable by addition of alkylene oxides (i.e., epoxy alkanes) to an intiating hydroxy substituted organic compound in which the hydroxy substituent is bonded to a carbon atom of the organic compound. As mentioned previously, these hydroxy organic compounds encompass the chain-extending or chain-blocking radicals discussed above. Thus, various 1,2-alkylene oxides such as 1,2-propylene oxide, 1,2-butylene oxide, 1,2-hexylene oxide, 1,2-dodecylene oxide, cyclohexyl ethylene oxide, etc., and styrene oxide, or mixtures thereof, or together with not more than '50 mole percent ethylene oxide, basis total moles of alkylene oxide, may be polymerized by contact with a basic or acidic catalyst in the presence of an initiating hydroxy organic compound. The aforementioned 1,2-alkylene oxides may be copolymerized with 1,3- and 1,4-alkylene oxides by acid catalytic polymerization in the presence of an initiating hydroxy organic compound, prov1ded however, that at least 50 mole percent of the alkylene oxide reacted possess a monovalent hydrocarbon moiety bonded to a carbon atom directly attached to an oxygen atom forming the epoxy ring. Illustrative of various 1,3- and 1,4-alkylene oxides include 1,3-propylene oxide, 1,4-butylene oxide (tetrahydrofuran), 1,4-pentylene oxide, 1,4-octylene oxide, etc., and 1,4-epoxy-2-phenyl butane, and the like.

The initiating hydroxy organic compound may be any one of the polyols previously described and include 1,2-

alkylene glycol, 1,3-alkylene glycol, 1,4-alkylene glycol, alkylene triols, alkylene tetrols, alkylene pentols, alkylene hexols, polyalkylene glycols, etc. Illustrative of these materials include ethylene glycol, 1,2- and 1,3-dihydroxypropane, 1,2- 1,3- and 1,4-dihydroxybutane, 1,2-, 1,3- and 1,4-dihydroxypentane, 1,2-, 1,3- and 1,4-dihydroxyhexane, 1,2-, 1,3- and 1,4-dihydroxydecane, 1,2-, 1,3- and 1,4-dihydroxyoctadecane, and the alpha, omega diols of the above hydrocarbon moieties not indicated as such. Polyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- and 1,3-dipropylene glycol, 1,2- and 1,3-tripropylene glycol, 1,2-, 1,3- and 1,4-dibutylene glycol, 1,2-, 1,3-, and 1,4-tributylene glycol, etc. Triols which may be utilized as the initiating hydroxy organic compound include glycerol, trimethylol propane, 1,2,3-trihydroxybutane, 1,2,3-trihydroxypentane, 1,2,3-trihydroxyoctane, 1,2,3-trihydroxydecane, 1,2,4-trihydroxybutane, 1,2,4-trihydroxyhexane, 1,2,6-trihydroxyhexane, 1,2,8-trihydroxyoctane, and the like. Illustrative of other polyols' which are suitable initiators includesorbitol, pentaerythritol, erythritol, aromatic hydroxy compounds of the formula:

and the like, and the saturated (nonbenzenoid) derivatives thereof; various other carbohydrates such as monosaccharides and polysaccharides, e.g., cellulose; starch; glucosides, such as the lower alkyl ('1 to 6 carbon atoms) glucosides, e.g. methyl-D-arabinoside, methyl-D-xyloside, ethyl-D-xyloside, n-butyl-D-riboside, methyl, ethyl, propyl, butyl, and Z-ethylhexyl-D-glycoside, 2-ethylhexyl-D- fructoside, isobutyl-D-mannoside, ethyl-D-galactoside, benzyl-D-glucoside and methyl-L-rhammoside; sucrose; glucose glycoside, maltose; lactose; 'D-glucose; D-iodose; hydroxyethyl cellulose; amylose; amylopectin; dextrin; and the like.

The initiator may also be any carbon-bonded monohydroxy organic compound, whether an actual alcohol or not. Inclusive of monohydroxy alcohols are the normal or branched chain alkanols such as methanol, ethanol, npropanol, isopropanol, n-butanol, sec.-butanol, tert.-bu tanol, n-pentanol, 2-pentanol, 3-pentauol, tert.-pentanol, n-octanol, 2-ethyl hexanol, and the like; and cycloaliphatic alcohols such as cyclobutanol, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, and the like. In addition, included are aromatic hydroxy compounds such as phenol and the like; and the alkyl substituted phenols, e.g., p-methyl phenol, l-hydroxy-3,5-di'- methyl benzene, and the like; aralkanols such as benzyl alcohol, hydroxy ethyl benzene and the like. In addition, there may be employed monohydroxy glycols, such as monoether glycols, e.g., monomethyl ether of ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, di-1,2- and 1,3-propylene glycol, the butylene and polybutylene glycols, and the like; other similar ethers such as, alkyl (1 to 4 carbon atoms), cycloalkyl (5 to 7 carbon atoms), aryl, alkaryl, aralkyl, etc., mono-ethers of the aforementioned glycols.

Desirably, theinitiator is admixed with the alkylene oxide in a liquid phase and the basic or'acidic catalyst is dispersed throughout this phase. Suitable'basic catalysts include alkali metal hydroxidessuch as sodium hydroxide and potassium hydroxide. Desirable acidic catalysts in clude Lewis acids such as boron trifluoride, aluminum chloride and the like. The catalyst is added in catalytic amounts, i.e., amounts sufiicient to effect reaction between the alkylene oxide and the initiating hydroxylated compound. When the catalyst is alkali metal hydroxide, amounts of from about 0.2 to 1.0 percent by weight of the alkylene oxide reacta'nt is convenient. When the catalyst is a Lewis acid, such as boron trifluoride, amounts of from about 0.01 to 1.0 percent by weight of the alkylene oxide reactant are suitable. The reaction can be effected at temperatures of from C. to aboutl60 C. and advantageously under pressures ranging from about 5 to 50 pounds per square inch'gauge. The reaction is preferably carried out under essentially moisture free (anhydrous) conditions to minimize side reactions. The addition of the alkylene oxide is terminated when the calculated quantities thereof have been introduced into the system. i v

The above process to form the'hydroxylated adducts is well understood by the art and forms no part of this invention. The resulting hydroxylatedadduct from the aforementioned reaction is often a mixture of molecules of varying molecular weights. These mixtures are suitable for preparing the novel beta-cyanoalkyl ethers of this invention. The average. molecular weight of the adduct is ascertainable by the acetylation of the various hydroxy groups.

A further embodiment of the invention involves a most useful method for the purification of the aforementioned cyanoalkylated compounds. Since the process for the reaction of the ethylenically unsaturated nitrile compounds and the hydroxylated ether adduct is effected in the presence of a basic catalyst, a portion of the ethylenically unsaturated nitrile, such as in the case of acrylonitrile, methacrylonitrile, etc., is typically caused to polymerize whereby to form an impurity of polymerized nitrile (hydrocarbon polynitrile) such as polyacrylonitrile and polymethacrylonitrile. This polymer may exist predominantly as a block copolymer of acrylonitrile and polyether adduct rather than as a true homopolymer.

Ordinarily, the presence of polyacrylonitrile per se would be of little concern in the manufacture of low.

molecular weight cyanoethylated compounds because they are purifiable by distillation. However, cyanoalkylation of the aforementioned hydroxylated polyether adducts yield products which are ,not readily purified by distillation particularly due to their excessively high boiling points. Moreover, the cyanoalkylated compounds of this invention are often not thermally stable at elevated temperatures close to their boiling points reverting to the alcohol and ethylenically unsaturated nitrile. In addition, the polyacrylonitrile is soluble in the cyanoalkylated products of this invention and also exhibit similar chemical characteristics. Hence, complete removal of the polyacrylonitrile by known separation methods such as crystallization, absorption, filtration and the like is not practical.

In addition to the above, it was unexpectedly found that the presence of the polymerized nitrile impurity in the cyanoalkylated product serves to poison the hydrogenation catalyst when the cyanoalkylated product is reduced to the corresponding amine derivative. Thus, hydrogenation is rendered difficult and expensive, necessi tating special techniques and uneconomically high C3121,- lyst concentrations. It is apparent that it is desirable to remove such polymerized nitrile impurities for the purpose of the hydrogenation process described herein in the manufacture of the corresponding amines of this invention.

Purification of beta-cyanoalkyl ether products, such as described above, is readily effected by forming a mixture of a beta-cyanoalkyl ether product and an inert liquid organic solvent in which the ether product is soluble and in which the polymerized ethylenically unsaturated nitrile, (polynitrile) such as polyacrylonitrile, polymethacrylonitrile, etc., is insoluble and precipitates. The solution of the ether product is separatedfrom the polynitrile precipitate and thereafter the pure ether product is readily recovered from the solvent by, for example, evaporation of the solvent. Y I I The beta-cyanoalkyl ether products of' this invention having a molecular weight in excess of about 450 typically possess sufficient hydrophobic characteristics as'contrast'ed with the more hydrophilic lower molecular weight species so that they are readily dissolved in the solvent 'to effect this purification process. The lower molecular weight species (below about 450)'of'the aforementioned ethers are not readily purified in accordance with the technique herein described. i p

In general, the solvents employed in the practice of the present invention will not necessarily be the same for each compound. In order to obtain optimum purification, the solvent or solvent combination should be appropriately chosen for each cyanoalkylated ether product. For example, the cyanoethylated derivative of polypropyleneglycol having a molecular weight of about 2025 was found to be soluble in pentane, hexane, and heptane but immiscible with isooctane or nonane.

The solvents which have been'fourid suitable for use in the practice of this invention are the saturated aliphatic and cycloaliphatic hydrocarbons having boiling points of from about 20 C., and lower, to about 160 C., and higher, determined at atmospheric pressure, more preferably from about 25 C. to about 100 C., and containing up to about 10 carbon atoms, and more preferably from about to about 9 carbon atoms. When the lower molecular weight hydrocarbons are employed which have boiling points below 20 C. at atmospheric pressure, the instant purification process can be conducted at superatmospheric pressures sufiicient to maintain the solvent in liquid form. Suitable solvents include, the alkanes'and cycloalkanes, such as, propane, butane, pentane, hexane, heptane, octane, nonane, cyclohexane, methylcyclohexane, dimethylcyclohexane, tetralin, decalin, the petroleum ethers, and the like.'Preferred solvents include pentane, hexane, heptane, octane, nonane, and cyclohexane. Particularly preferred'solvents are pentane, hexane, heptane, and cyclohexane.

Inasmuch as the cyanoalkylated polyoxyalkylene products in the preferred molecular weight range, but at the lower portion thereof, i.e. from about 450 to about 1000, sometimes cannot be satisfactorily purified with an aliphatic or cycloaliphatic hydrocarbon alone, due to their limited solubility, it is often desirable to -employ a cosolvent. The co-solventmust, 'of'course, be'capable of effecting complete solution of the solvent and the cyanoalkylated product without also dissolving the polyethylenically unsaturated nitrile, e.g.,. polyacrylonitrile, or adversely affecting the cyanoalkylated produc Suitable cosolvents which can be employed in conjunction with the aforementioned aliphatic or cycloaliphatic hydrocarbon solvents are those having boiling points within the aforesaid range, 'i.e., from about 20 C. to about 160 C., more preferably fromabout 25 C. to about 100 C., and containing up to 12 carbon atoms or more, preferably up to carbonatoms. The cosolvent should have a greater polarity than the solvent. As indicated above for the hydrocarbon solvents, the use of the lower molecular weight cosolvents,.i.e.,-those having boiling points below 20 C., may require that the process be conducted at superatmospheric pressures. 7

Typical cosolvents include the aliphatic, cycloaliphatic and aromatic ethers, including mixtures thereof, such as, dimethyl ether, methyl'ethyl ether, diethyl ether, di-npropyl ether, diisopropyl ether, methylrn-butyl ether,

ethyl-n-butyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, di-n-hexyl ether, ethylene glycol dimethyl ether, dicyclohexyl ether, methyl cyclohexyl ether, ethyl cyclohexyl ether, anisole; the aliphatic, cycloaliphatic and aromatic esters including mixtures thereof, such as, methyl formate, ethyl formate, diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, methyl-n-butyrate, ethyl-n-butyrate, methyln-valerate, methyl isovalerate, methyl cyclohexyl carboxylate, ethyl cyclohexyl carboxylate, methyl benzoate, ethyl benzoate; aliphatic, cycloaliphatic and aromatic acetals and ketals, including mixtures thereof, such as acetaldehyde dimethyl acetal, acetaldehyde diethyl acetal, acetaldehyde methyl ethyl acetal, acetaldehyde di-n-butyl acetal, propionaldehyde dimethyl acetal, propionaldehyde diethyl acetal benzaldehyde dimethyl acetal, acetone ethyl phenethyl acetal; aliphatic ketones, such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, methyl-t-butyl ketone, diisopropyl ketone; aliphatic and cycloaliphatic alcohols, such as methyl alcohol, .ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, t-amyl alcohol, cyclohexanol; aliphatic and cycloaliphatic amines, including mixtures thereof, such as, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, n-butylamine, n-amylamine, cyclohexylamine; aliphatic, cycloaliphatic, and aromatic hydrocarbons, including alkyl-substituted derivatives thereof, such as, pentane, cyclohexane, benzene, toluene, xylene, tetralin, decalin; heterocyclic compounds such as, tetrahydrofuran, and the like; halogenated aliphatic hydrocarbons such as, carbon tetrachloride, chloroform, perchloroethylene and the like.

Preferred cosolvents include ethyl formate, ethyl acetate, ethyl propionate, ethyl carbonate, diethyl acetal, diethyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethyl alcohol, isopropyl alcohol, t-butyl alcohol, triethylamine, carbon tetrachloride, chloroform, tetrahydrofuran, anisole, benzene, toluene and Xylene. The particularly preferred cosolvents include diethyl ether, dibutyl other, ethyl acetate, and tetrahydrofuran.

In some instances where the hydrocarbon solvent alone will satisfactorily effect dissolution of the cyanoethylated product, it maystill be desirable for economic considerations to employ a cosolvent. Moreover, a second hydrocarbon solvent is sometimes suitable for use as the cosolvent.

In general, theproportion of solvent to the cyanoalkylated product should be such that all of the cyanoalkylated product is dissolved. The actual amount of solvent will,,of course, vary depending upon the particular product being purified, the solvent employed, and other considerations. As a general rule, the proportion of solvent to the cyanoalkylated product should be in a weight ratio of at least 1.5 to 1. In those instances where cosolvents are used, the hydrocarbon solvent should be the major component of the solvent mixture, basis weight of' the mixture, to ensure that none of the polyethylenlcally unsaturated nitriles, e.g., polyacrylonitrile, dissolves. Typically, the hydrocarbon component in the solvent mixture at least equals, andpreferably exceeds, the weight of the, cyanoalkylated product. It is thus preferred to employ only those solvent mixtures which consist. of at least 50 weight percent of hydrocarbon solvent and up to 50 weight percent of cosolvent, basis weight of the solvent mixture.

To obtain maximum separation of the cyanoalkylated product from the polyunsaturated nitrile, it is preferred to employ a ratio, in parts by weight, of hydrocarbon solvent to cyanoalkylated product of at least 2 to 1 and more, preferably of at least 3 to 1, when the hydrocarbon solvent is employed alone. When the hydrocarbon solvent is utilized in conjunction with a cosolvent it is preferred to em- 1 l ploy a weight ratio of hydrocarbon solvent to cyanoalkylated product of from about 1 to 1 to about 5 to 1, and more preferably from about 1.5 to 1 to about 2.5 to 1.

Upon dissolution of the cyanoalkylated product in the hydrocarbon solvent or solvent mixture, the polyunsaturated nitrile is precipitated as a solid. The solvent and precipitate are then separated by conventional methods, such as, decantation, oentrifugation, filtration, and the like. If the polyunsaturated nitrile precipitate is gelatinous or sticky, it is advisable to use a filter aid if filtration is employed as the means of separation. Magnesol (a commercial magnesium silicate), charcoal, kieselguhr, and other commercially available filter aids are suitable for this purpose.

Subsequent removal of the hydrocarbon solvent or solvent mixture by evaporation leaves the purified cyanoalkylated product typically as an almost colorless to colorless oil. The purified product can then be catalytically reduced to the corresponding primary amine with lower hydrogenating pressures and catalyst concentrations than those necessary for the unpurified product, particularly when hydrogenation is effected as described herein. Moreover, the catalyst remains active and can be reused in subsequent hydrogenation reactions.

As indicated above, the beta-cyanoalkyl ether products are suitable for the production of the corresponding amine through reduction of the nitrile moieties thereof. Thus, the above discussion relating to the structure of the beta-cyanoalkyl ether products equally applies to the gammaaminoalkyl ether derivative obtained by hydrogenation.

Such com-pounds may be more specifically characterized by the following formula:

wherein A, Q, X, X v, p and r are as described previously.

The gamma-aminoalkyl products of this invention are obtainable by conventional hydrogenation of the corresponding beta-cyanoalkyl products in such cases where the beta-cyanoalkyl products are in substantially pure state, e.g., as obtained from the aforedescribed purification process. However, there has been found a novel method by which hydrogenation of the beta-cyanoalkyl ether prod ucts may be gainfully effected even though the products contain substantial amounts of the polymerized nitrile impurity. This method has been found to significantly overcome the catalyst poisoning effect of the polymerized nitrile impuritiy. In addition, this novel hydrogenation method may be successfully employed in the hydrogenation of the purified beta-cyanoalkyl ether products obtainable by, e.g., the afore-described purification process.

It is known that some nitrile ethers are cleaved at the ether linkage during hydrogenation. The problem of cleavage is found to be exceedingly acute during hydrogenation of cyanoethylated polyoxyalkylene products such as bis cyanoethylated polypropylene glycols having molecular weights between 200 and 2100. The hydrogenation of these compounds over nickel catalysts is invariably accompanied by appreciable cleavage when solvents containing easily detachable protons are employed. Attempted hydrogenation without a solvent or with a hydrocarbon solvent such as cyclohexane is, for the most part, unsatisfactory in that very little of the nitrile is reduced. Moreover, since purification by distillation of the 3-aminopropyl derivatives of polypropylene glycols having molecular weights greater than about 330 is found to be impractical due to their excessively high boiling points, it becomes im portant to devise methods to eliminate or substantially reduce cleavage and hence impurity formation, occurring during the reaction.

It is found that hydrogenation of beta-cyanoalkylated derivatives of polyoxyalkylene compounds may be effected with appreciable reduction in the cleavage problem and, in many cases, with complete elimination of the problem, by hydrogenating the nitriles in the presence of a ternary amine and optionally, but preferably, in the further presence of anhydrous ammonia.

The effect of the amines in minimizing cleavage is unexpected inasmuch as these amines are bases which might be expected to promote the cleavage. In addition to the re duction of the cleavage problem these particular amines alone or with ammonia enhance the rapidity of the hydrogenation reaction and also allow for a reduction in hydrogenation pressures over those typically utilized with other solvent systems. Moreover, the hydrogenated product is substantially colorless or is only faintly colored.

The hydrogenation process of this invention is desirably effected by dissolving the beta-cyanoalkyl polyalkylene oxide products in a tertiary amine, with or without anhydrous ammonia, adding the hydrogenation catalyst and hydrogenating the mixture. Recovery and isolation of the amine reaction product is readily effected by filtering off the catalyst and thereafter stripping the solvent from the filtrate.

In pracice, it is preferred to employ anhydrous ammonia in conjunction with the tertiary amine. It has been observed that the conjunctive use of anhydrous ammonia with the amine solvent system increases the purity of the reaction product. Moreover, it has been found that when anhydrous ammonia is used cleavage of the cyanoalkyl product is almost completely inhibited and the color of the resulting product is enhanced.

The advantages obtained by conducting the reaction in the presence of a tertiary amine willbe apparent from a comparison of the reduction of alpha, omega-bis(2-cyanoethyl ether) of poly-1,2-propylene glycol in tertiary butanol with reductions in triethylamine as indicated in Table I which follows. Not only was the purity of the product superior when the tertiary amine was used but the hydrogenation proceeded more rapidly and at a lower pressure, that is, at about 1000 pounds per square inch gauge. The difference between the values quoted for total base content and primary amino nitrogen is a measure of the secondary amine present since only trace amounts of tertiary amine were found in the product.

TABLE I.PREPARATION OF 0:, m-BIS(3-AMINOPROPOXY)POLY-1,2-PROPYLENE GLYCOL BY REDUCTION OF a,w-BIS(2-CYANOETHER) OF POLY-1,2-PROPYLENE GLYCOL EFFECT OF SOLVENT B Analyses of product b Time required for Primary Reaction uptake of Total-base amino tempcra- Hydrogenatlng hydrogen, content, nitrogen Example Solvent ture, 0. pressure, p.s.i.g. mius. meq./g. meq./g.

1 t-Butanol 120 1, 0002, 000 210 0. 706 0. 601 2 Triethylamine 120 1, 000-2, 000 0. 758 0. 652 3 .do 120 ,000 52 0. 738 0. 580 4 110 1, 000-2, 000 0. 152 0. 141 5 1, 000 45 0. 707 0. 600

a Each experiment done by hydrogenating a mixture of equal weights of u,w-bis(2 cyanoethoxy)poly-1,2 propylene glycol having an approximate molecular weight of 2,131 and the indicated solvent with 15 weight percent of the total charge of a nickel on kieselguhr catalyst containing about 65 weight percent of nickel.

b a,w-Bis(3-aminopropoxy)poly-1 nitrogen content of 0.935 meq.

,2-propylene glycol has a calculated total-base content and primary amino 9 Determined by the method of F. E. Critchfield and J. B. Johnson, Anal. Chem., 29, 1174 (1957).

TABLE II.PREPARATION OF a,w-BIS(3-AMINOPROPOXY) POLY-1,2-PROPYLENE GLYCOL BY REDUCTION OF ego-BIS(2-CYANOETHOXY)POLY-1,2-PROPYLENE GLYCOL EFFECT OF ANHYDROUS AMMONIA Analyses of Product b Time Goncen- Hydrorequired Primary tration of genating for uptake Total-base amino catalyst, pressure, of hydrocontent, nitrogen, Example wt. percent p.s.i.g. gen, mins. meq./g. meq./g.

e In each experiment a mixture of equal weights of a,w-bis(2-cyanoethoxy)poly-1,2-propylcne glycol having a molecular weight of 2131 and triethylamine was hydrogenated at 120 C. in the presence of a nickel on kieselguhr catalyst.

b 0:,w-BlS (B-aminopropoxy)poly-1,2-propylene glycol has a calculated total-base content and a primary amino nitrogen content of 0.935 meq./g.

Deter-mined by the method of F. E. Critchfield and J. B. Johnson, Anal. Chem. 29, 1174 (1957).

d Anhydrous ammonia added in an amount equal to one-quarter of the weight of the cyano-compound.

Anhydrous ammonia added in an amount equal to one-third of the weight of the cyano-compounds.

In general, the tertiary amines employed in the instant process encompass tertiary alkyl or aryl amines and heterocyclic tertiary amines. In particular, amines having boiling points of below 250 C. at atmospheric pressure and not being easily susceptible to hydrogenolytic fission can be utilized.

The tertiary amines include those compounds characterized by the formulae:

wherein X is an integer of from 2 to 6, and R R and R;, may each represent alkyl groups containing from 1 to 8 carbon atoms, cycloalkyl groups containingfrom 4 to 8 carbon atoms, or phenyl groups, withthe provision that the amines do not contain more than one phenyl -R s, particularly the R.,s, need not be the same throughout the molecule. Two of the Rs, e.g., R", and

R R and R and R and R,, may be joined to form a-divalent alkylene radical of from 2 to 10 carbon atoms.

1 Suitable tertiary amines which fulfill the aforementioned requirements include, among others, trimethylamine, triethylamine, tripropylamine, tri-n-butylamine, triamylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylbutylamine, N,N-dimethylamylamine, N,N- dim'ethylethylamine, N,N-dimethylpropylarnine, N,N-diethylpropylamine, N,N-diethylbutylamine, N,N-dipropylbutylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, pyridine, alpha-picoline, 3,5-lutidine, 2,4;6-collidine, N,N-dimethylaniline, N,N'-dimethylpiperazine and the like. Particularly preferred amines of the aforementioned group include triethylamine and pyridine.

'The concentration of the amine in the reaction system is not necessarily critical and all that is needed is an amount sufficient to substantially inhibit cleavage of the cyanoalkylated compound during the reduction process. For practical purposes, the lowest effective weight concentration of the amine is about 5 percent, basis weight of the cyano-compound. Excessive cleavage typically occurs below this concentration. The upper limit of amine concentration will largely be determined by economic and other considerations. However, for most practical purposes an amine concentration, based on the weight of cyanoalkyl product, of from 10 to 50 percent is preferred. Table IV, which follows, illustrates the effect of the amine concentration.

Inasmuch as the catalytic reduction process of the present invention is influenced by other process variables, these will be considered in their relation to the preparation of the oxyalkylamines from the corresponding cyanoalkylated ether products.

The effectiveness of several hydrogenation catalysts was investigated to determine those most capable of effecting the reduction of the cyanoalkylated products under the conditions of the present invention. In practice, it was discovered that the nickel catalysts were the most suitable. Illustrative catalysts include, nickel, Raney nickel, supported nickel and supported nickel-containing catalysts. For example, supported nickel catalysts include among others, nickel on kieselguhr, nickel on fullers earth, nickel on clay, and the like. Preferred catalysts applicable for use in the present invention consist of reduced and stabilized nickel on a kieselguhr support, particularly those containing from about 50 to about weight percent nickel. A particularly preferred catalyst consists of reduced and stabilized nickel on a kieselguhr support containing approximately 65 weight percent nickel. Other catalysts such as cobalt on kieselguhr and palladium on carbon, though useable, have group per molecule. P3 may be hydrogen or R The 55 not proven as elfective as the above described catalysts.

TABLE V.-PREPARAT1ON OF age-BIS (3AMINOPROPYLETHER) OF POLY- l,2-PROPYLENE GLYCOL BY REDUCTION OF a,w-BIS(2-CYANOETHOXY) POLY-1,2-PROPYLENE GLYOOL EFFECT OF THE NATURE OF THE CATALYST ON THE HYDRO GENATION B Analyses of product b e E'achexperiment was done by hydrogenating at C. a mixture of equal weights of a,u-bis(2-cyanoethoxy) poly-1,2-propylene glycol having a molecular weight of 2,131 and triethylamine with the catalyst in an amount equal to 30 weight percent of the cyanocompound. Anhydrous ammonia was also added.

a-m-Bis(3-aminopropoxy)poly-1,2-prcpylene glycol has a calculated total-base content andprimary amino nitrogen content of 0.935 meq. g.

g Washed with anhydrous ethanol then with triethylamine.

ad Anhydrous ammonia added in an amount equal to one-third of the weight of the cyanocompound.

" Cobalt on kieselguhr; Co eontent=50 percent by weight of the catalyst. f Anhydrous ammonia added in an amount equal to one-quarter of the weight of the cyano- 8 compound.

operating conditions for one catalyst may not necessarily be the same for another.

Although reaction temperatures of from about 75 to 150 C. are possible, it is preferred to conduct the hydrogenation at temperatures within the range of from about 110 to about 130 C., and still more preferably from' about 115 C. to about 125 C. While the hydrogenation reaction will proceed at temperatures above and below the aforementioned broad range, the purity of the product is likely to be lower.

In order to obtain satisfactory yields of the gammaaminoalkyl ether products which have an acceptable degree of purity, hydrogenation pressures in excess of 120 pounds per square inch gauge are employed. Pressures in excess of 500 pounds per square inch gauge, and more preferably within the range of from about 950 to about 2000 pounds per square inch gauge have found to provide enhanced conversion and maximum purity. The upper limit of the hydrogenating pressure will largely be determined by economic considerations.

Although the tertiary amine can be employed alone, the use of anhydrous ammonia in conjunction with the tertiary amine provides optimum conversion, maximum inhibition of cleavage, and results in a product which is essentially colorless or only faintly colored. The actual concentration of ammonia of course, will be in-part dependent upon the amount of the tertiary or heterocyclic amine present. However for practical purposes a concentration of anhydrous ammonia, based on the weight of cyano-product, of up to 3 weight percent and more, preferably up to 25 weight percent can be employed. When the hydrogenation reaction was conducted in the presence of anhydrous ammonia, but in the absence of a tertiary or heterocyclic amine, the purity of the product was low indicating possible cleavage at the ether linkage. It is therefore preferred to use the anhydrous ammonia only in conjunction with the tertiary amine.

The cyanoalkylated products should be neutralized by the addition of an equivalent quantity of a mineral acid, such as phosphoric acid to eliminate residual basic catalyst prior to reduction by the instant hydrogenation process. Cleavage of the nitrile will otherwise ocur if the basic catalyst is not essentially eliminated.

The gamma-aminoalkyl ether products produced by the process of the instant invention are useful as components of polyurethane elastomers, polyurethane foams, flexible and rigid polyamide resins, epoxy resin hardeners, and the like.

The following enumerated examples merely illustrate operations of the inventions described herein and are not intended to limit the scope of the inventions in any manner. All percentages in these examples are by weight unless otherwise indicated.

EXAMPLE 1 The following illustrates the production of u-(2-cyanoe'thoxy)-w-(n-butyl)poly-1,2-oxypropylene by the reaction of acrylonitrile with mono-n-butanol ether of polyis stirred and contains 0.28 weight percent water and 0.13

weight percent NaOH. 135.4 grams of acrylonitrile is fed to the mixture over a 2-hour period. The temperature of the mixture is maintained by occasional cooling at 25 C. to 30 C. The maximum degree of cyanoethylation as determined by infra-red analysis is achieved 3% hours after all the acrylonitrile addition is completed. The mixture is neutralized by addition of 10.4 grams of weight percent aqueous phosphoric acid. The neutralized mixture is evaporated at a temperature not exceeding C. under progressively reduced pressure (from 200 to 20 millimeters Hg) until a residue is formed which no longer exhibits weight loss. Comparative infrared scans show that cyanoethylation is 93 weight percent complete.

EXAMPLE 2 The following illustrates the purification of the cyanoethylated product produced in Example 1:

884 grams of the cyanoethylated product of Example 1 is dissolved in 3000 grams of anhydrous, sulfur-free heptane at 25 C. Within 60 minutes after solution, most of the polyacrylonitrile is determined to have settled out of solution, leaving a slightly hazy supernatant liquid. No further change in the solution is noted after standing overnight. The supernatant liquid is decanted and the remaining suspension of polyacrylonitrile is filtered through a kieselguhr-coated filter. The residue of polyacrylonitrile on the filter is washed with heptane. The washing is combined with the filtrate and added to the supernatant liquid. The liquid is stirred 5 minutes with the addition of 26.5 grams of Magnesol (magnesium silicate) and then filtered through a kieselguhr-coated filter to give a clear, colorless, filtrate. The filtrate is evaporated at a temperature not exceeding 100 C. under reduced pressure (from 200 to 20 millimeters Hg) to a constant weight. The resulting liquid product is shown by infrared analysis to contain 93.4 weight percent a-(2-cyanoethoxy)-w-(nbutyl poly-1,2-oxypropylene.

EXAMPLE 3 The following illustrates the production of a,w-biS(2- cyanoethoxy)-poly-1,2-oxybutylene by the reaction of acrylonitrile with poly-1,2-butylene glycol having an average molecular weight of 500:

1.0 gram of sodium methoxide is added to 1500 grams of poly-1,2-butylene glycol having an average molecular weight of 500. The glycol is covered by an atmosphere of nitrogen. The water content of the glycol, by the Karl Fisher method, is 0.067 weight percent and the sodium methoxide content of the glycol-sodium methoxide mixture by acidimetric titration is 0.053 weight percent. 558 grams of acrylonitrile is continuously added over two hours with stirring to the glycol-sodium methoxide mixture, the temperature of the reaction being kept between 25 C. to 30 C. by occasional cooling. 52 minutes after completion of acrylonitrile addition, it is noted from infrared analysis that cyanoethylation is complete. The sodium methoxide is neutralized by the addition of 3 grams of 85 weight percent aqueous phosphoric acid. The product is stripped under reduced pressure with a kettle temperature not exceeding 100 C. to a constant weight. 96 weight percent of the residue consisted of cyanoethylated product.

EXAMPLE 4 The following illustrates the separation of the product produced in Example 3.

1000 grams of the cyanoethylated product of Example 3 is dissolved in 4000 grams of anhydrous, sulphur-free heptane at 25 C. Most of the polyacrylonitrile is found to settle out within 30 minutes from formation of the solution. There is no further change on standing overnight at 25 C. The solution is decanted and the remaining polyacrylonitrile suspension is filtered through a kieselguhrcoated filter. Filtration is found to be rapid, indicating a fairly large particle size for the polyacrylonitrile. The residue of polyacrylonitrile on the filter is washed once with heptane. The washing is combined with the filtrate and added to the decanted liquid. The whole liquid is stirred 15 minutes with 20 grams of Magnesol (magnesium silicate) at 25 'C. and the mixture is filtered through a kieselguhr-coated filter to give a clear and colorless liquid. Evaporation to a constant weight of the filtrate under reduced pressure with a kettle temperature not exceeding 100 C. leaves 945 grams of a clear, almost colorless oil, which by infrared analysis, contains 96.3 weight percent of the a,w-bis(2-cyanoethoxy)-poly-1,2- oxybutylene.

EXAMPLE 5 The following illustrates the preparation of ot,w-biS-(2- cyanoethoxy)-poly-1,2-oxybutylene from the reaction of acrylonitrile with poly-1,2-butylene glycol having an average molecular Weight of 1000. The procedure of Example 3 is followed, using the following diiferent amounts of ingredients:

Ingredient: Amount in grams Sodium methoxide 1.0 1000 M.W. poly-1,2-butylene glycol 1500.0 Acrylonitrile 3 12.5 85 weight percent aqueous phosphoric acid 3.2

The obtained residue product exhibits 96.6 weight percent cyanoethylated product. When the residue product is treated according to the procedure described in Example 4, there is obtained 839 grams of a clear, pale-straw oil which, from infrared analysis contains 95.7 weight percent of the a,w-bi.s(2-cyanoethoxy)-poly-1,2-oxybutylene.

EXAMPLE 6 The following illustrates the preparation of a,w-biS(2- cyanoethoxy)-poly-1,2-oxybutylene from the reaction of acrylonitrile with poly-1,2-butylene glycol having an average molecular weight of 2,000:

The procedure described in Example 3 is employed using the following different amounts of ingredients:

Ingredient: Amount in grams Sodium methoxide 1.0 2000 M.W. poly-1,2-butylene glycol 1500. Acrylonitrile 159.0 85 weight percent aqueous phosphoric acid 3.2

The obtained residue product contains 92.9 weight percent cyanoethylated product. When the residue product is treated according to the procedure described in Example 4, there is obtained 914.0 grams of a pale-yellow oil which, from infrared analysis, comprises 92.5 weight percent of the e o-bis(2-cyanoethoxy)poly-1,2-oxybutylene. It is to be noted that in the purification of the residue product according to the procedure of Example 4, little polyacrylonitrile settles from the heptane solution. Accordingly, filtration through the kieselguhr-coated filter is achieved with some difficulty. However, mixture of the filtrate the Magnesol allows ready filtration.

EXAMPLE 7 The following illustratesthe production of ot,w-bi$(2- cyanotheoxy)-poly-1,2-oxypropylene by the reaction of acrylonitrile with poly-1,2-propyleneglycol having an average molecular weight of 1025 212.2 grams of acrylonitrile is added over two hours with stirring to a mixture of 1103.0 grams of poly-1,2- propylene glycol having an average molecular weight of 1025 and 5.5 grams of aqueous 20 weight percent sodium hydroxide covered by an atmosphere of nitrogen. The exothermic reaction is kept between 25 C. and 30 C. by occasional cooling. The reaction is noted to be complete through infrared analysis about four hours after completion of acrylonitrile addition. The sodium hydroxide is neutralized by addition of 2.0 grams of aqueous 85 weight percent phosphoric acid. Excess of acrylonitrile and traces of water are removed by stripping the product to a constant weight under reduced pressure with a kettle 18 temperature not exceeding 100 C. There remains a hazy yellow oil.

A 500 gram portion of this oil is stirred 30 minutes at 50 C. with 50.0 grams of Magnesol and thenis filtered through a kieselguhr-coated filter to obtain a clear, almost colorless filtrate which is evaporated under reduced pressure at a temperature not exceeding 100 C. until the residue no longer loses weight. There remains an almost colorless oil which by infrared analysis contains 96.4 weight percent of the c m-bis(2 cyanoethoxy)poly- 1,2-oxypropylene.

EXAMPLE 8 The following illustrates production of oz, w-biS(2- cyano-ethoxy)-poly-1,2-oxypropylene by the reaction of acrylonitrile with poly-1, 2-oxypropylene glycol having an average molecular weight of 2025:

The procedure described in Example 7 is employed using the following different amounts of ingredients:

Ingredients: Amounts in grams Acrylonitrile 638.8 Poly-1,2-oxypropylene glycol 2025 M.W. 6075.0 Aqueous 20 weight percent NaOH 30.0 Aqueous weight percent phosphoric acid- 10.8

The product obtained is a clear, almost colorless oil containing 94 weight percent of the u,w-bis(2-cyanoethoxy -poly-l ,2-oxypropylene.

EXAMPLE 9 The following illustrates the production of 1,2,6-tris- [ot-(2-cyanoethoxy)-poly-1,2-oxypropyl]hexane by the reaction of acrylonitrile with the triol formed from the oxypyropylation of 1,2,6-hexanetriol, which triol has an average molecular weight of 4950 and a hydroxyl number of 34.

79.6 grams of acrylonitrile are added over two hours with stirring to a mixture of 1,298 grams of the triol and 3.8 grams of aqueous 20 weight percent NaOH covered by an atmosphere of nitrogen gas. The reaction, which is exothermic, is kept between 25 C. and 30 C. by occasional cooling. The reaction is noted to be complete through infrared analysis about 4% hoursafter completing addition of the acrylonitrile. The NaOH is neutralized by addition of 1.4 grams of aqueous 85 weight percent phosphoric acid. Excess of acrylonitrile and water are removed by stripping the product to a constant weight under reduced pressure with a kettle temperature 1101; exceeding C., resulting in a hazy yellow oil. 500.grams of the oil arestirred for 30 minutes at 50 C. with 50.0 grams of Magnesol and then filtered through a kieselguhrcoated filter. The filtrate is a clear, colorless oil containing 92 weight percent of the 1,2,6-tris[a-(2-cyanoethoxy)- poly-1,2-oxypropylene1hexane. I

EXAMPLE 10 The following illustrates the production of 1,2,3-tris- [a-(2-cyanoethoxy)-poly-1,2-oxypropyl1propane, by the reaction of acrylonitrile with the triol formed by, the

oxypropylation of glycerine', which triol has fan average molecular weight of 3000 and a hydroxyl numberg ofl-56: The procedure described in Example 9..is employed using the following different amounts of ingredients;

Ingredients: I Amounts in grams Acrylonitrile 159.2 Aqueous 20 weight percent NaOH 1.... 7.5 Triol- "-1480 Aqueous 85 weight percent phosphoric acid; A 2.7

The following illustrates the production of='a,ai-bis(2- cyanoethoxy) poly 1,2 oxypropylene-1,4 oxybutyl- 19 ene (50/50) by the reaction of acrylonitrile with a copolymer glycol of 50 mol percent 1,2-oxyproplyene and 50 mol percent 1,4-xybutlyene, which glycol has an average molecular weight of 1500 and a hydroxyl number of 45:

To a mixture of 250 grams of the glycol and 0.8 grams of sodium methoxide there is added with stirring over a two hour period 21.2 grams of acrylonitrile. The reaction temperature is maintained between 25 C. and 30 C. by occasional cooling. Maximum cyanoethylation as determined by infrared analysis is achieved 25 minutes after termination of acrylonitrile addition. The mixture is neutralized by addition of 2.6 grams of aqueous 85 weight percent phosphoric acid. The neutralized mixture is evaporated to a constant weight at a temperature not exceeding 100 C. under progressively reduced pressure (from 200 to 20 millimeters Hg). Comparative infrared scans shows that cyanoethylation is 95.6 weight percent complete EXAMPLE 12 The following illustrates the preparation of tris(2- cyanoethyl)-ether of oxypropylated tris(4-hydroxyphenyl) propane by the reaction of acrylonitrile with the triol formed by oxypropylating a mixture of 1,1,3- and 1,1,2-tris(4-hydroxyphenyl) propane, which triol has a hydroxyl number of 259 and an average molecular weight of 650.

1,500 grams of the triol is dissolved in 500 grams of pyridine and 7.5 grams of aqueous 20 weight percent sodium hydroxide is mixed therewith. The pyridine acts as a solvent for the viscous triol. A nitrogen gas atmosphere is maintained over the mixture. 735 grams of acrylonitrile is stirred into the mixture over a two-hour addition period. The reaction temperature through occasional cooling is maintained between 25 C. and 30 C. The maximum degree of cyanoethylation is noted from infrared analysis to occur 3 hours after completion of acrylonitrile addition. The NaOH is neutralized by the addition acid. Pyridine, water and excess acrylonitrile are removed by stripping the product until a constant weight is achieved under reduced pressure with a kettle temperature not exceeding 100 C. The residue product is a pale brown, viscous oil and, from infrared analysis, exhibits complete cyanoethylation.

EXAMPLE 13 Ingredients: Amounts in grams Hexol 1,983 Acrylonitrile 972 Pyridine 300 Aqueous 20 weight percent NaOH 8.0 Aqueous 85 weight percent H PO 8.6

The residue product is a pale brown, viscous oil and, from infrared analysis, exhibits complete cyanoethylation.

EXAMPLES 14-52 To demonstrate the effectiveness of the solvent purification process, four grams of the cyanoethylated product is dissolved in the solvent or solvent mixtures indicated in Table VI below. The whole is then centrifuged. When the hydrocarbon solvent or solvent mixture is satisfactory, polyacrylonitrile readily separates and quickly settles to the bottom of the centrifuge tube leaving a homogeneous clear and colorless, supernatant liquid.

The treated products are the dicyanoethylated derivatives of polypropylene :glycols which have molecular weights of 425, 1025 and 2025 and which are designated in Table VI as compounds A, B, and C respectively. These products are made by the process described in Exof 6.5 grams of aqueous 85 weight percent phosphoric 40 amples 7 and 8.

TABLE VI.PURIFICATION OF CYANOETHYLATED COMPOUNDS BY HYDROCARBON SOLVENTS AND SOLVENT MIXTURES Weight, grams Com- Weight, Example pound Pentane Hexane Heptaue Octane Co-solvent gms. Rating I 2 5 2 2 2 1 2 2 2 3 2 3 6 5 do 2 3 6 Oyclohexane 2 1 do- 20 1 Methyl cyclohexane 16 2 10 Anisole. 2 3 9 Diethyl acetal- 2 2 9 Ethyl acetate 1. 8 1 9 Methyl ethyl ketone- 1. 6 2 8 Carbon tetrachloiide. 2 2 8 n-Butyl ether- 1. 4 1 6 Ethyl formate- 1 8 6 -do- 2. 2 3 8 Ethyl propionate 1. 6 2 8 'Ietrahydroiuran 1. 7 1 6 Amtnne 2, 3 2 Chloroiorm 1 3 (1O 2 3 Isopropyl ether. 2. 5 2 -do 1. 6 3 Ethyl carbonate.. 4 3 Triethylaruine- 1. 6 2 t-Butanol. 2 2 2 3 2 2 2 3 1.8 1 3. 2 ,1 2. 3 1 3 N0nane 6} 1 3 Ethyl acetate. 1 51 C 7 Butyl ether 2 2 52 C 7 --do 2 2 n 1=Exeellen t separation of pelyacrylonitrile; 2=Good separation of polyacrylonit rile; 8= Fair separation of polyacrylorutrile; 4=Peor separation of polyacrylonitrile; 5=No separation-of polyacryletdttilex ZUxification method failed.

21 EXAMPLE 53 220 grams of the residue product obtained by treating a polypropylene glycol having an average molecular weight of about 425 with acrylonitrile in the presence of a basic catalyst, in accordance with the procedures of Examples 7 and'8, is dissolved at 25 C. in a mixture of 220 grams of commercial, sulphur-free hexane and 220 grams of anhydrous diethyl ether. A yellow, flocculent precipitate of polyacrylonitrile rapidly separates. The mixture is stirred for minutes with 11.0 grams of Magnesol and then is filtered through a kieselguhr-coated filter. The filtrate is homogeneous, clear, and almost colorless. It is evaporated first at atmospheric then under reduced pressure at a temperature below 100 C. until the residue no longer loses weight. There remains a clear, light-yellow oil. The original product is yellow and opaque.

1400 grams of the purified cyanoethylated derivative, 1400 grams of isopropyl alcohol and Raney nickel (233.3 g. of aqueous sludge washed four times with isopropyl alcohol before use) are introduced into a 2-gallon, stainless steel autoclave provided with a stirrer. The free space is purged of air with hydrogen, 350 grams of anhydrous ammonia is added, and then the pressure in the autoclave is increased to 300 pounds per square inch gauge, by the addition of hydrogen.

The mixture is heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge, by the addition of more hydrogen. The temperature is kept at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen has ceased (75 minutes) and thereafter for 30 minutes.

After removal of the catalyst by filtration, the reaction product is evaporated first at atmospheric then under reduced pressure at a temperature below 100 C. until the residue no longer loses weight. Bis(3-aminopropyl)ether of poly-1,2-propylene glycol remains as a clear, strawcolored oil having a faint ammoniacal odor. .The product has a total alkalinity of 3.57 milliequivalents per gram and it contains 3.50 milliequivalents per gram of primary amino nitrogen. Based on its primary amino nitrogen content, the diamine has a purity of about 95 percent.

When original cyanoethylated derivative prior to solvent treatment is treated with hydrogen under the same conditions as the purified derivative but with a'reaction time of 75 minutes (there is no evident uptake of hydrogen) the reaction product, after working up as before, is a light brown oil. It has a total alkalinity of 1.515 milliequivalents per gram and it contains 1.445 milliequivalents per gram of primary amino nitrogen. Furthermore, analysis shows that the product contains 2.215 milliequivalents per gram of nitrile groups which indicates that about 60 percent of the original nitrile groups have not been reduced.

p 7, EXAMPLE 54 1000 grams of the residue product obtained by treating a polypropylene glycol having a-molecular weight of about 1025 with acrylonitrile in the presence of a basic catalyst as shown in Example 7 is dissolved at 25 C. in a mixture of 1680 grams of commercial sulphur-free hexane and 400 grams anhydrous diethyl ether. A yellow, flocculent precipitate of polyacrylonitrile separates. The mixture is stirred for 15 minutes with 50 grams of Magnesol (a commercial magnesium silicate) and then is filtered through a kieselguhr-coated filter. The filtrate is homogeneous, clear, and colorless. It is evaporated first at atmospheric then under reduced pressure with a kettle temperature not exceeding 100 C. until the residue no longer loses weight. There remains a clear and colorless oil. The original product is yellow and opaque.

300.0 grams of the purified cyanoethylated derivative, 300.0 grams of triethylamine, and 30.0 grams of Girdler G-49A catalyst 1 are introduced into a l-gallon, stainless 1 A nickel on kleselguhr catalyst containing 65 weight percent of nickel.

steel autoclave fitted with a stirrer. The free space is purged of air with hydrogen, 75 grams anhydrous ammonia is added, and then the pressure in the autoclave is increased to 300 pounds per square inch gauge by the addi-.

tion of hydrogen. The mixture is heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge by the addition of more hydrogen. The temperature is kept at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen ceases, about 10 minutes, and thereafter for 30 minutes. After removal of the catalyst by filtration, the reaction product is evaporated first at atmospheric then under reduced pressure at a temperature below C. until the residue no longer loses weight. The reaction product remains as an almost colorless oil having a faint ammoniacal odor. It has a total alkalinity of 1.279 milliequivalents per gram and it contains 1.257 milliequivalents per gram of primary amino nitrogen. Based on the primary amino nitrogen content the diamine has a purity of about 76 percent.

When the original cyanoethylated derivative is treated with hydrogen under the same conditions as the purified derivative but with a reaction time of 1 hour 45 minutes the reaction product, after working up as before, is a yellow oil. It has a total-alkalinity of 0.496 milliequivalent per gram and it contains 0.340 milliequivalent per gram of primary amino nitrogen. Furthermore, analysis shows the product to contain 1.287 milliequivalents per gram of nitrile group which indicates that about 78 percent of the original nitrile groups have not been reduced.

EXAMPLE 55 1245 grams of the residue product obtained by treating a polypropylene glycol having a molecular weight of about 2025 with acrylonitrile in the presence of a basic catalyst, as shown in Example 8, is dissolved at 25 C. in 4,980 milliliters of commercial, sulphur-free hexane. A yelloworange flocculent precipitate of polyacrylonitrile separates. The mixture is allowed to settle overnight; then the clear, faintly yellow supernatant liquor is filtered through paper. After being stirred at 25 C. for 30 minutes with 62.3 grams of Magnesol the filtrate is filtered through a kieselguhr-coated filtere. The filtrate from this last operation is colorless; it is evaporated first at atmospheric then under reduced pressure at a temperature below 80 C. until the residue no longer loses weight. There remains aclear, colorless and viscous liquid. The original crude product is orange and opaque.

400.0 grams of the purified cyanoethylated derivative, 400.0 grams of triethylamine and 40.0 grams of Girdler G-49A catalyst are introduced into a one-gallon, stainless steel autoclave fitted with a stirrer. The free space is purged of air with hydrogen after which the mixture is heated to C. and the pressure increased to 150 pounds per square inch gauge by the addition of hydrogen.

The temperature is kept at 120 C. and the hydrogenating pressure at to pounds per square inch gauge until uptake of hydrogen has ceased, about 15 minutes, and thereafter for 30 minutes. After removal of the catalyst by filtration, the reaction product is evaporated first at atmospheric pressure then under reduced pressure at a temperature below 100 C. until the residue no longer loses weight. a,w-Bis(3-aminopropoxy)-poly-1,2-oxypropylene remains as a light brown oil having a faint ammoniacal odor. It has a total-alkalinity of 0.801 milliequivalent per gram and it contains 0.601 milliequivalent per gram of primary amino nitrogen. Based on its primary amino nitrogen content, the diamine has a purity of about 65 percent.

When the original cyanoethylated derivative is treated with hydrogen under the same conditions as the purified derivative the reaction product, after working up as before, is a light greenish-brown oil. It has a total-alkalinity of 0.27 milliequivalent per gram and it contains 0.265

23 milliequivalent per gram of primary amino nitrogen. Furthermore, analysis shows the product to contain 0.60 milliequivalent per gram of nitrile groups which indicates that about 64 percent of the original nitrile groups have not been reduced.

EXAMPLE 56 330.0 grams of the purified cyanoethylated derivative of Example 55, 330 grams isopropyl alcohol, and 55.0 grams of Raney nickel (aqueous sludge, washed four times with isopropyl alcohol before use) are introduced into a one-gallon, stainless steel autoclave provided with a stirrer. The free space is purged of air with hydrogen, 82.5 grams of anhydrous ammonia is added, and then the pressure in the autoclave is increased to 300 pounds per square inch gauge by the addition of hydrogen. The mixture is heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge by the addition of more hydrogen. The temperature is kept at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen ceases, about 45 minutes, and thereafter for 30 minutes. Work ing up of the product as in the previous example affords the a,w-bis(3-aminopropyl)ether of poly-1,2-propylene glycol as a colorless oil. It has a total alkalinity of 0.884 milliequivalent per gram and contains 0.880 milliequivalent per gram of primary amino nitrogen. Based on its primary amino nitrogen content, the diamine has a purity of about 94 percent.

When the original cyanoethylated derivative is treated with hydrogen under the same conditions as the purified derivative, the reaction product, after working up as before, is an orange oil. It has a total-alkalinity of 0.250 milliequivalent per gram and contains 0227 milliequivalent per gram of primary amino nitrogen. Furthermore, analysis shows that the product contains 0.737 milliequivalent per gram of nitrile groups which indicates that about 79 percent of the original nitrile groups have not been reduced.

EXAMPLE 57 500 grams of a residue product, obtained by cyanoethylation as illustrated in Example of a triol made by the oxypropylation of glycerol and having a hydroxyl number of 56, is dissolved at 25 C. in 2000 cc. of commercial hexane. Polyacrylonitrile separates as a flocculent yellow precipitate. The mixture is allowed to settle overnight; then the clear supernatant liquid is decanted from the olyacrylonitrile and stirred for minutes with grams of Magnesol. The Magnesol is removed by filtration through a kieselguhr-coated filter and the colorless filtrate is evaporated to a constant weight first at atmospheric then under reduced pressure at a temperature not exceeding 80 C. There remains a clear and colorless oil. The original crude product is yellow and opaque.

300.0 grams of the purified cyanoethylated derivative, 300.0 grams of isopropyl alcohol, and 50.0 grams of Raney nickel (aqueous sludge, washed four times with isopropyl alcohol before use) are introduced into a l-gallon, stainless steel autoclave provided with a stirrer. The free space is purged of air with hydrogen, 75 grams of anhydrous ammonia are added, and then the pressure in the autoclave is increased to 300 pounds per square inch gauge by the addition of hydrogen. The mixture is heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge by the addition of more hydrogen. The temperature is kept at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen ceases, about 15 minutes, and thereafter for minutes. After removal of the catalyst by filtration, the reaction product is evaporated to a constant weight first at atmospheric then under reduced pressure at a temperature below 100 C. Tris(3-aminopropyl)ether of polyoxypropyl'g'ycerol remains as a clear and colorless oil having a faint ammoniacel odor. It has a total alkalinity of 0.854

24 milliequivalent per gram and contains 0.844 milliequivalent per gram of primary amino nitrogen. Based on the primary amino nitrogen content, the triamine has'a purity of 88 percent.

When the original cyanoethylated derivative is treated with hydrogen under the same conditions as the purified derivative but with a reaction time of one hour the reaction product, after working up as before, is a yellowbrown oil. It has a total-alkalinity of 0.258 milliequivalent per gram and it contains 0.231 milliequivalent per gram of primary amino nitrogen. Furthermore, analysis shows that the product contains 0.690 milliequivalent per gram of nitrile groups which indicates that 72.1 percent of the original nitrile groups have not been reduced.

EXAMPLE 58 500 grams of the hazy yellow oil of Example 9 is dissolved at 25 C. in 2000 cc. of commercial, sulphur-free hexane.

The mixture is stirred for 15 minutes with 25 grams of Magnesol and then filtered through a kieselguhr coated filter. This operation is then repeated. The final filtrate is homogeneous, clear, and very pale yellow. It is evapo: rated to a constant weight first at atmospheric then under reduced pressure at a temperature below 100 C. There remains a clear, yellow oil.

EXAMPLE 59 487.7 grams of the residue product obtained by treating the monobutyl ether of polypropylene glycol with acrylonitrile in the presence of a basic catalyst as described in Example 1 is dissolved in 1463.1 grams of anhydrous, sulfur-free heptane. The mixture is stirred for 15 minutes at room temperature (25 C.) with 14.6 grams of Magnesol and then filtered through a Kieselguhr coated filter. Filtration is easy and rapid. The clear, almost colorless filtrate is evaporated to a constant weight under reduced pressure with a kettle temperature below 100 C. There remains 454.3 grams of a clear, yellow oil which appears by infrared, analysis to be cyanoethylated to the extent of 96.3 percent.

EXAMPLE 60 250 grams of alpha, omega-bis(2-cyanoethoxy)poly- 1,2-oxypropylene, characterized by an average molecular weight of 2131 and having a purity of 94- percent, 250 grams of triethylamine, and 75.0 grams of a reduced and stabilized nickel on kieselguhr catalyst weight percent nickel) are introduced into a three liter, stainless steel autoclave equipped with a stirring device. The free space is purged of air with hydrogen, 62.5 grams of anhydrous ammonia added, and the pressure in the autoclave increased to 300 pounds per square inch gauge by the addition of hydrogen. Thereafter, the mixture is heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge by the addition of more hydrogen. During the reaction the pressure is maintained at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen ceases and thereafter for an additional thirty minutes.

1 The monobutyl ether of polypropylene glycol has the formula:

(CH: C4H9O HCHZO 11H wherein n=approxlmately 6.2

and contains 0.841 milliequivalent per gram of primary amino nitrogen, as determined by the method of F. E. Critchfield and I. B. Johnson, Anal. Chem., 29 1174 (1957).

EXAMPLE 61 The procedure employed in Example 60 is repeated except that the quantity of triethylamine employed is reduced to one-tenth of the weight of the alpha, omegabis(2 cyanoethoxy)poly-1,2-oxypropylene. The resulting alpha, omega-bis 3-aminopropoxy) poly-1,2-oxypropylene is a colorless oil. It has a total-alkalinity of 0.831 milliequivalent per gram and contains 0.812 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 62 The procedure employed in Example 60 is repeated in the absence of the anhydrous ammonia. The resulting alpha, omega bis(3 aminopropoxy)poly 1,2 oxypropylene is an apple-green oil. The product has a total alkalinity of 0.738 milliequivalent per gram and contains 0.580 milliequivalent per gram of primary amino nitrogen.

EXAMPLE. 63

316 grams of alpha, omega-bis(2-cyanoethoxy)poly- 1,2-oxy-propylene, having an average molecular weight of 2135 and a purity of 94 percent, 316 grams of triethylamine, and 94.8 grams of commercial Raney nickel (which has been washed first with anhydrous ethanol then with triethylamine) are introduced into a three-liter stainless steel autoclave equipped with a stirring device. The free space is purged of air with hydrogen, 106 grams of anhydrous ammonia added, and the pressure in the autoclave is increased to 300 pounds per square inch gauge by the addition of hydrogen. The mixture is then heated to 120 C. whereupon the pressure is further increased to 1000 pounds per square inch gauge by the addition of more hydrogen. The temperature is maintained at 120 C. and the hydrogenating pressure at 950 to 1000 pounds per square inch gauge until uptake of hydrogen ceases and thereafter for 30 minutes.

'After removal of the catalyst by filtration, the reaction product is evaporated to a constant weight first at atmospheric pressure then under a reduced pressure at a temperature below 100 C. The resulting alpha, omegabis(3-aminopropoxy)poly-1,2-oxypropylene remains an an almost colorless oil having a faint ammoniacal odor. The product has a total-alkalinity of 0.931 milliequivalent per gram and contains 0.912 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 64 The procedure employed in Example 60 is repeated except that an equal weight ofreduced and stabilized cobalt on kieselguhr catalyst (containing about 50 percent cobalt) was substituted for the nickel or kieselguhr catalyst. The alpha, omega-bis(3-aminopropoxy)poly;1,2- oxypropylene produced is a straw-colored oil which has a total alkalinity of 0.712 milliequivalent per gram and contains 0.678 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 65 The procedure employed in Example 60 is repeated except that an equal weight of pyridine is substituted for the triethylamine. The alpha, omega-bis(3-aminopropoxy)poly-1,2-oxypropylene produced is a pale-yellow oil. The product has a total-alkalinity of 0.857 milliequivalent per gram and contains 0.838 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 66 The procedure employed in Example 60 is repeated except that an equal weight of N,N,N',N'-tetramethyl- 1,3-butanediamine is substituted for the triethylamine. The alpha, omega-bis(3-aminopropyl)ether of poly-1,2-

propylene glycol produced is a pale, straw-colored oil. The product has a total-alkalinity of 0.840 milliequivalent per gram and contains 0.791 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 67 The procedure employed in Example 60 is repeated except that an equal weight of tri-n-butylamine is substituted for the triethylamine. The resulting alpha, omegabis(3-aminopropyl)ether of poly-1,2-propylene glycol having an average molecular weight of 2139' is produced as a pale-yellow oil. The product has a total-alkalinity of 0.925 milliequivalent per gram and it contains 0.751 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 68 The procedure employed in Example 60 is repeated except that an equal weight of N,N-dimethylaniline is substituted for the triethylamine. The resulting alpha, omega-bis( 3 aminopropoxy)poly-1,2-oxypropylene having an average molecular weight of 2139 is a pale-straw colored oil. The product has a total-alkalinity of 1.095 milliequivalents per gram and contains 0.817 milliequivalent per gram of primary amino nitrogen.

EXAMPLE 69 Tricyanoethylated polyoxypropyl-l,2,6-trihydroxyhexane (having a purity of about 92 percent and obtained by cyanoethylation of a triol having a hydroxyl number of 34 made by oxypropylation of 1,2,6-trihydroxyhexane) as shown in Examples 9 and 5 8 is hydrogenated according to the procedure given in Example 60. After removal of the catalyst by filtration, the reaction product is evaporated to a constant weight first at amospheric then under reduced pressure at a temperature below C. Tris- (3-aminopropoxy)polyoxypropyl 1,2,6 trihydroxyhexane remains as an almost colorless oil having a faint ammoniacal odor. The product has a total-alkalinity of 0.482 milliequivalent per gram and contains 0.458 milliequivalent per gram of primary amino nitrogen. Based on the primary amino nitrogen content the triamine has a purity of 82.0 percent.

EXAMPLE 70 Tricyanoethylated polyoxypropylglycerol (having a purity of about 91 percent and obtained bycyanoethylation of a triol having a hydroxyl number of 56 made by oxypropylation of glycerol) is hydrogenated according to the procedure given in Example 60. After removal of the catalyst by filtration, the reaction product is evaporated to a constant weight first at atmospheric then under reduced pressure at a temperature below 100 C. Tris(3- aminopropyl)ether of polyoxypropylglycerol remains as an almost colorless oil having a faint ammoniacal odor. The product has a total-alkalinity of 0.845 milliequivalent per gram and contains 0825 milliequivalent per gram of primary amino nitrogen. Based on the primary amino nitrogen content the triamine has a purity of 83.5 percent.

EXAMPLE 71 Tricyanoethylated polyoxypropylglycerol (having a purity of about 91 percent and obtained by cyanoethylation of a triol having a hydroxyl number of 640 made by oxypropylation of glycerol) is hydrogenated according to the procedure given in Example 60. After removal of the catalyst by filtration, the reaction product is evaporated to a constant weight first at atmospheric then under reduced pressure at a temperature below 100 C. Tris(3- aminopropyl)polyoxypropylglycerol remains as a yellow oil having a faint ammoniacal odor. The product has a total-alkalinity and primary amino nitrogen content of 5.18 milliequivalents per gram. Based on the primary amino nitrogen content the triamine has a purity of 87.8 percent.

EXAMPLE 72 Tricyanoethylated polyoxypropyl 1,1,3 tris(4 hydroxyphenyl)propane [obtained by cyanoethylation of a triol having a hydroxyl number of 259-and made by the union of approximately 6 moles of propylene oxide with 1 mole of 1,1,3-tris(4-hydroxyphenyl)propane as described in Example 12] is hydrogenated according to the procedure given in Example 60. After removal of the catalyst by filtration, the reaction product is evaporated first at atmospheric then under reduced pressure at a tem perature below 100 C. until the residue no longer loses weight. Tris(3-aminopropyl)polyoxypropyl.- 1,1,3 tris- (4-hydroxyphenyl)propane remains as a pale-brown oil having a faintammoniacal odor. The product has a totalalkalinity of 3.21 milliequivalents per gram and contains 3.14 milliequivalents per gram of primary amino nitrogen. Based on the primary amino nitrogen content the triamine has a purity of 81.6 percent.

Various modifications and embodiments of the inventions described herein can be made without departing from the spirit and scope thereof. Although the preceding specifically illustrates the inventions'herein, such is not to be construed as limiting the scope of the inventions except when set forth in the claims.

What is claimed is:

1. A compound of the formula:

(a) R is hydrogen or an alkyl group having from 1 to about 4 carbon atoms.

(b) {-R O),, is an oxyhydrocarbylene group having a molecular weight of from about 20,000 consisting of: (i) one or more oxyalkylene groups containing from 3 to about 12 carbon atoms, or (ii) a mixture of one or more oxyalkylene groups containing from 3 to about 12 carbon atoms and not more than about 50 mole percent ethyleneoxy radicals.

(c) m is an integer from 1 to 8,

(d) y is an integer from 0 to 10.

2. 1,2,6 tris[a-(3-aminopropoxy) -poly-1,2-oxypropyl] hexane of the formula:

CH2 CHQCHINHZ l2 wherein n, w and z are positive integers the sum of which is from about 8 to about 250.

3. The compound of' claim 2 where the 1,2,6-tris(poly- 1,2-oxypropyl)hexane moiety has an average molecular weight of about 4950.

4. 1,2,3-tris[ot-(3-aminopropoxy)-poly-1,2 oxypropyl] propane, the 1,2,3-tris (poly-1,2-oxypropyl)propane moiety thereof having an average molecular weight of from about 450 to about 20,000.

5.- 1,2,3-tris[a-(3-aminopropoxy)-poly-1,2 oxypropyl] propane, the 1,2,3-tris(poly-1,2-oxypropyl)propane moiety thereof having an average molecular weight of about 3,000.

6. In a process for the hydrogenation of a compound selected from the group consisting of a-(2-cyanoalkoxy)- w (hydrocarbyl)-polyoxyhydrocarbylene; a,w-bis-(2-cyanoalkoxy)-polyoxyhydrocarbylene and tris-(Z-cyanoalkoxy) terminated polyoxyhydrocarbylene to form the corresponding amine, wherein: 1

(a) said polyoxyhydrocarbylene has an everage molecular Weight of from about 450m about 20,000, (b) said alkoxy is a group containing from about 2 to about.10 carbon atoms, (c) said hydrocarbyl is an alkyl group containing from 1 to about 8 carbon atoms,- and (d) said oxyhydrocarbylene is:

from 3' to about 12 carbon atoms, or v .(ii) a mixture ofone or more oxyalkylene groups containing from 3 to about 12 carbon atoms and not more than about 50 mole percent ethyl eneoxy radicals, the improvement which comprises hydrogenating said compound at a temperature of from about 75 C. to about 150 C. and a pressure of from about p.s.i.g.to about 2,000 p.s.i.'g. in'the presence of a nickel, palladium or. cobalt catalyst and (a) one or more tertiary amines characterized by the formulae:

wherein is an integer of from 2 to 6; R Rg and R may be the same or difierent and represent alkyl groups containing from 1 to 8 carbon atoms, cycloalkyl groups containing from. 4 to 8 carbon atoms or phenyl with the proviso that said amines may not containmore than one phenyl group per molecule; R may be hydrogen or R and where two of said radicals may be joined together to form a divalent alkylene radical, or (b) a mixture of one or more of said tertiary amines and anhydrous ammonia. 7. The method of claim 6 where said cyanoalkylated compound is 1,2,6-tris[a-(2-cyanoethoxy)-poly-1,2-oxypropyl] hexane of the'formula:

CH3 CH; O- (iIHCHzO CHaCH: CN

(i) one or more oxyalkylene groups containing,

10. In a process for the hydrogenation of an a-(2-cyan0 alkoxy) w (hydrocarbyl-polyoxyhydrocarbylene compound to form the corresponding amine, wherein:

(a) said polyoxyhydrocarbylene has an average molecular weight of from about 450 to about 20,000,

(b) said alkoxy is a group containing from about 2 to about carbon atoms,

(c) said hydrocarbyl is an alkyl group containing from 1 to about 8 carbon atoms, and ((1) said oxyhydrocarbylene is:

(i) one or more oxyalkylene groups containing from 3 to about 12 carbon atoms, or (ii) a mixture of one or more oxyalkylene groups containing from 3 to about 13 carbon atoms and not more than about 50 mole percent ethyleneoxy radicals, the improvement which comprises hydrogenating said compound at a temperature of from about 75 C. to about 150 C. and a pressure of from about 120 p.s.i.g. to about 2,000 p.s.i.g. in the presence of a nickel, palladium or cobalt catalyst and (a) one or more tertiary amines characterized by the formulae:

N-Rs R4 wherein x is an integer of from 2 to 6; R R and R may be the same or ditferent and represent alkyl groups containing from 1 to 8 carbon atoms, cycloalkyl groups containing from 4 to 8 carbon atoms or phenyl with the proviso that said amines may not contain more than one phenyl group per molceule; R may be hydrogen or R and where two of said radicals may be joined together to form a divalent alkylene radical, or

(b) a mixture of one or more of said tertiary amines and anhydrous ammonia.

11. The method of claim 10 where said amine is selected from a member of the group, trimethylamine, triethylamine, tripropylamine, tri-n-butylamine, triamylamine, N,N,N,N'-tetramethyl-1,3-butanediamine, N,N-dimethylbutylamine, N,N-dimethylamylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-diethylpropylamine, N,Ndiethylbutylamine, N,N-dipropylbutylamine, N,N dimethylcyclohexylamine, N,N-diethylcyclohexylamine, pyridine, alpha-picoline, 3,5-1utidine, 2,4,6-collidine, N,N-dimethylaniline, or N,N'-dimethylpiperazine.

12. The method of claim 10 where said compound is a-(Z-cyanO-ethoXy-w-(n-butyl)-poly-l,2-oxypropylene.

13. In a process for the hydrogenation of an a o-bis- (Z-cyanoalkoxy) -polyoxyhydrocarbylene compound to form the corresponding amine, wherein:

(a) said polyoxyhydrocarbylene has an average molecular weight of from about 450 to about 20,000,

(b) said alkoxy is a group containing from about 2 to about 10 carbon atoms,

(c) said hydrocarbyl is an alkyl group containing from 1 to about 8 carbon atoms, and (d) said oxyhydrocarbylene is:

(i) one or more oxyalkylene groups containing from 3 to about 12 carbon atoms, or (ii) a mixture of one or more oxyalkylene groups containing from 3 to about 12 carbon atoms and not more than about 50 mole percent ethyleneoxy radicals, the improvement which comprises hydrogenating said compound at a temperature of from -about'75 C. to about 150 C. and a pressure of from about 120 p.s.i.g.

to about 2,000 p.s.i.g. in the presence of a nickel, palladium or cobalt catalyst and (a) one or more tertiary amines characterized by the formulae:

wherein x is an integer of from 2 to 6; RH, R and R may be the same or different and represent alkyl groups containing from 1 to 8 carbon atoms, cycloalkyl groups containing from 4 to 8 carbon atoms or phenyl with the provisio that said amines may not contain more than one phenyl group per mole; R .may be hydrogen or R and where two of said radicals may be joined together to form a divalent alkylene radical, or

(b) a mixture of one or more of said tertiary amines and anhydrous ammonia.

14. The method of claim 13 where said compound is a,w-(2-cyanoethoxy)-poly 1,2 oxybutylene where said poly-1,2-oxybutylene moiety has an average molecular weight of from about 450 to about 20,000.

15. The method of claim 13 where said cyanoalkylated compound is a-arbis-(2-cyanoethoxy)-poly-1,2-oxypropylene where said poly-1,2-oxypropylene moiety has an average molecular weight of from about 450 to about 20,000.

16. The method of claim 13 where said cyanoalkylated compound is m-w-bis-(Z-cyanoethoxy)-poly-1,2-oxypropylene-1,4-oxybutylene where said poly-1,2-oxypropylene- 1,4-oxybutylene moiety has an average molecular weight of from about 450 to about 20,000.

17. In a process for the hydrogenation of a compound having the formula:

wherein:

(a) R is hydrogen or alkyl having from 1 to about 4 carbon atoms,

(b) (R -O) is a divalent polyoxyhydrocarbylene group having an average molecular weight of from about 450 to about 20,000 consisting of:

(i) one or more oxyalkylene groups containing from 3 to about 12 carbon atoms, or,

(ii) a mixture of one or more oxyalkylene groups containing from 3 to about 12 carbon atoms and not more than about 50 mole percent ethyleneoxy radicals,

(c)-R is an alkylene group containing from 2 to about 10 carbon atoms,

(d) m is an integer from 0 to 8,

(e) y is an integer from 0 to 10.

the improvement which comprises hydrogenating said compound at a temperature of from about 75 C. to about 150 C. and a pressure of from about p.s.i.g. to about 2,000 p.s.i.g. in the presence of a nickel, palladium or cobalt catalyst and (a) one or more tertiary amines characterized by the N I N\ R4 R": wherein x is an integer of from 2 to 6; RH, R and R may be the same or dilferent and represent alkyl groups containing from 1 to 8 carbon atoms, -oyclo alkyl groups containing from 4 to 8- carbon atoms or phenyl with the proviso=that said amines may not contain more than one phenyl group per molecule; R", may be hydrogen or R and-where two of said radicals may be joined together to form a divalent alkylene radical, or (b) a mixture of one or more of said tertiary amines and anhydrous ammonia. 1

References Cited UNITED STATES PATENTS 32 Wilkes et al. 260584 Lambrech 260584 X Shivers 260-584 UX Speranza et al. 260584 Prescott et al 2605 84 UK Lee et a1. 260-584 Lehmann et a1. 260570.7 X De Vries 260584 Reinking 260584 X Little 260570.7 Feldman et a1 2605 83 Miller et al 260584 X Little et a1 260570.7 X

FOREIGN PATENTS FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

25247.5, 54.6; 2602 BP, 77.5 B, 77.5 AQ, 465 F, 465.6, 563 R, 570.5 P, 570.7, 615 B 9 UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3799986 Issue Date March 26 1974 Inven tor a) Fedor Poppelsdorf It is certified that error appeara 1n the above-identified patent and that said Letter: Patent are hereby corrected aa ahown below:

Column 1,91ine 5s, "leat", should read least Column 7 line 26, in the formula:

should read,

Column 12, a line 40, pracice" should read practice Column 14, after line 31 insert TABLE IV (copy attached) Y UNITED STATES PATENT omcn CERTIFICATE OF CORRECTION March 26, .1974

Patent No. 3799986 Issue Date Inventofla) 'Fedbr pp o I Page 3 It is cort'ifiod that error appears in the, above-idhtified potent and that aid Lotto" Potent are hereby corroctod u ohown below:

Column 13, line 22, under column which reads "Pota1-base content meg./g. 0.841

Column '15-, line 41, "3" should read 33 Column 22 line 44, "filtere", should read filter Column 23,- line 73 p0lyoxypropylgycerol'' should read polyoxypropylglycerol I Column 23', v line 75, "ammoniacel" shouldread ammoniacal Y Column 25, line 46, "an? should read as Column 25, line 56, "or" should read on UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3799986 Issue Date March 26, 12M;

Inventofla) F dor Poppeladorf Page 4 It is certified that error appears in the above-identified patent and that said Lettere Patent are hereby corrected u shown below:

In the Claims Claim 1 coi. 27, line 37', after the word "about" insert i450 to about" Claim 2 C01. 27, 1am: portion of ormia,

line 59 ")2" should read ')z'.' Claim 13) C01. 30-, line 19' "mole" should read mo1ecu1e Signed and sealed this 24th day of September 1974.

(SEAL) Attest: v v MCCOY M'QGIBSON- JR. c. MARSH LL DANN Attesting Officer Commissioner of Patents 

